JPS58198856A - Manufacture of negative cadmium plate for alkaline storage battery - Google Patents
Manufacture of negative cadmium plate for alkaline storage batteryInfo
- Publication number
- JPS58198856A JPS58198856A JP57081915A JP8191582A JPS58198856A JP S58198856 A JPS58198856 A JP S58198856A JP 57081915 A JP57081915 A JP 57081915A JP 8191582 A JP8191582 A JP 8191582A JP S58198856 A JPS58198856 A JP S58198856A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- cadmium
- plate
- negative electrode
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/246—Cadmium electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【発明の詳細な説明】
本発明はアルカリ蓄電池用ペースト式カドミウム負極板
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a paste-type cadmium negative electrode plate for alkaline storage batteries.
近年、例えば密閉型アルカリ蓄電池においては、ニッケ
ル正極板の高容量化が進んでおり、また同時に、結果と
して電池内の正極板の占める体積も２ ・ 二
増大している。そこで、正極板の高容量化に伴って負極
活物質も増加しなければならないが、電池内容積の制限
から、負極活物質量を増加していくことは困難である。In recent years, for example, in sealed alkaline storage batteries, the capacity of nickel positive electrode plates has been increasing, and at the same time, the volume occupied by the positive electrode plates in the battery has increased by 2.2. Therefore, as the capacity of the positive electrode plate increases, the amount of negative electrode active material must also be increased, but it is difficult to increase the amount of negative electrode active material due to the limitation of battery internal volume.
このため負極活物質自体の利用率を向上していくことが
重要である。Therefore, it is important to improve the utilization rate of the negative electrode active material itself.
従来、特開昭５１−１３８８３１号に記載されているよ
うに、ペースト式カドミウム負極板の利用率向上を目的
として種々の金属粉末及び金属酸化物等が加えられてき
たが、いわゆる導電材としての役割が大であり、添加に
よる体積増加から昨今の正極容量の増加に対応しきれな
いのが現状である。Conventionally, various metal powders and metal oxides have been added for the purpose of improving the utilization rate of paste-type cadmium negative electrode plates, as described in JP-A-51-138831. It plays a major role, and the current situation is that it cannot cope with the recent increase in positive electrode capacity due to the increase in volume due to addition.
１だ特開昭５０−１６０了４８号に記載のように、ニッ
ケル等の多孔質基板に硝酸カドミウム等の活物質溶液を
含浸せしめ、その後アルカリ溶液中に浸漬、水洗、乾燥
して活物質を充填する方法において、活物質溶液にニッ
ケル塩を含有させたものもあるが、サイクル寿命に効果
があるものの、初期からの極板利用率には効果があられ
れていない。1. As described in JP-A No. 160-160-48, a porous substrate made of nickel or the like is impregnated with a solution of an active material such as cadmium nitrate, and then immersed in an alkaline solution, washed with water, and dried to remove the active material. Some filling methods include nickel salts added to the active material solution, but although this has an effect on cycle life, it does not have an effect on the initial plate utilization rate.
′ すなわち、負極に水酸化ニッケルを添加することに
より、充放電サイクル時に負極活物質である３ ページ
金属カドミウム及び水酸化カドミウム相互の電気化学的
変換を助ける作用がある。しかし、カドミウム塩とニッ
ケル塩の混液状態で多孔質基板に含浸後、アルカリ溶液
にて水酸化物化したものは、水酸化カドミウム粒子内に
水酸化ニッケルが取り込まれた状態にある。そして、化
成時に生成する金属カドミウムが、プレス加工時に金属
塊状に加圧凝集され、充放電サイクルによる溶解−析出
反応の繰返しで次第に水酸化ニッケルの効果が現われる
ものである。また焼飴式の場合は、金属多孔内に活物質
が充填されるため、金属カドミウムがプレスにより金属
塊化されにくいが、カドミウム塩とニッケル塩の混合水
溶液から水酸化カドミウムと水酸化ニッケルを析出、乾
燥、粉砕後、ペーストとし、負極板に加工した場合は金
属塊化が促進されるため、ニッケル添加の効果があられ
れない０
またペースト式負極の製造法ヤ、初期の練合物に水酸化
ニッケルを加えることによって高温保存性能、いわゆる
高温自己放電の抑制に効果があることも報告されている
が、水酸化ニッケルの添加方法として、練合物中に粉体
で混入するため、水酸化ニッケルの局在化を避けること
ができず、カドミウム活物質に周囲を覆われるため初期
からの負極板利用率の向上には効果が乏しい。また、水
酸化ニッケルの粒径についても精密な制御を必要とする
。That is, the addition of nickel hydroxide to the negative electrode has the effect of assisting the electrochemical conversion between the negative electrode active material, metal cadmium, and cadmium hydroxide during charging and discharging cycles. However, when a porous substrate is impregnated with a mixture of cadmium salt and nickel salt and then converted into hydroxide using an alkaline solution, nickel hydroxide is incorporated into the cadmium hydroxide particles. The metal cadmium produced during chemical formation is coagulated under pressure into a metal lump during press working, and the effects of nickel hydroxide gradually appear as the dissolution-precipitation reaction is repeated through charging and discharging cycles. In addition, in the case of the baking candy method, since the active material is filled into the metal pores, the metal cadmium is less likely to be turned into metal lumps by pressing, but cadmium hydroxide and nickel hydroxide are precipitated from a mixed aqueous solution of cadmium salt and nickel salt. After drying and pulverizing, if the paste is processed into a negative electrode plate, metal agglomeration will be promoted and the effect of nickel addition will not be achieved. It has also been reported that adding nickel oxide is effective in suppressing high-temperature storage performance, so-called high-temperature self-discharge. Localization of nickel cannot be avoided and the surrounding area is covered with cadmium active material, so there is little effect on improving the utilization rate of the negative electrode plate from the initial stage. Furthermore, the particle size of nickel hydroxide also requires precise control.
本発明は上記従来技術に鑑みてなされたもので、ニッケ
ル塩溶液にペースト式極板を浸漬し、次いで化成するた
め、極板全体に均一に水酸化ニッケルを添加することが
でき、顕著な利用率向上の効果が生じるものである。The present invention has been made in view of the above-mentioned conventional technology, and since a paste-type electrode plate is immersed in a nickel salt solution and then chemically formed, nickel hydroxide can be uniformly added to the entire electrode plate, and it can be used for remarkable purposes. This has the effect of improving the rate.
以下、本発明の実施例について説明する。Examples of the present invention will be described below.
〔実施例１〕
平均粒径１〜２μの酸化カドミウム粉末１０ｏｙと平均
粒径約２μのニッケル粉末２５ｙの混合物に、１ｙのポ
リビニルアルコールを溶解した４゜ＣＣのエチレングリ
・コール溶液を投入し、約６０分線合してペースト状と
する。このペーストを厚さα１岨のニッケル鍍鋼穿孔板
の両面に塗着しだの５ベージ
ち、１１０℃にて１時間乾燥する。ついでペーストの脱
落を防ぐ予備加圧を行なった後、１モル／℃の硫酸ニッ
ケル水溶液に浸漬し、８０℃で３０分間乾燥する。[Example 1] A 4° CC ethylene glycol solution in which 1 y of polyvinyl alcohol was dissolved was added to a mixture of 10 y of cadmium oxide powder with an average particle size of 1 to 2 μm and 25 y of nickel powder with an average particle size of about 2 μm, Blend for about 60 minutes to make a paste. This paste was applied to both sides of a nickel-plated steel perforated plate having a thickness of α1 mm for 5 pages, and then dried at 110° C. for 1 hour. After applying preliminary pressure to prevent the paste from falling off, it is immersed in a 1 mol/°C aqueous nickel sulfate solution and dried at 80°C for 30 minutes.
上記方法で得られたカドミウム負極板と、従来の方法で
得られた負極板すなわち、硫酸ニッケル水溶液に浸漬し
ないものを濃ｍ１２０ｗｔ％ のか性カリ水溶液中にお
いて、充電、放電を繰返し化成を施して活物質の利用率
を測定した。The cadmium negative electrode plate obtained by the above method and the negative electrode plate obtained by the conventional method, that is, those not immersed in a nickel sulfate aqueous solution, are subjected to chemical conversion by repeated charging and discharging in a concentrated 120 wt% aqueous caustic potassium solution. The utilization rate of the material was measured.
その結果を第１図に示す。図中（ａ）は硫酸ニッケルに
浸漬した本発明による負極の、（ｂ）は従来法による負
極板の利用率を示すものである。The results are shown in FIG. In the figure, (a) shows the utilization rate of the negative electrode according to the present invention immersed in nickel sulfate, and (b) shows the utilization rate of the negative electrode plate according to the conventional method.
第１図から明らかなように極板利用率の向上に関して本
発明では顕著な効果が見られる。As is clear from FIG. 1, the present invention has a remarkable effect on improving the utilization rate of electrode plates.
〔実施例２〕
実施例１と同様な方法で得られる負極板で、ペーストの
塗着重量、すなわち活物質容量を大幅に減少せしめたも
のに関して化成（ここでいう化成とはカドミウム負極板
の一部充電、あるいは充放電の繰返しによって一部に還
元部分を有するもの６ ベーン
をいう）を行なった後およそＱ ５ ｒｒａｎの厚さに
加圧して完成極板とする。[Example 2] A negative electrode plate obtained in the same manner as in Example 1, in which the applied weight of the paste, that is, the active material capacity, was significantly reduced, was chemically formed (here, chemically formed is a type of cadmium negative electrode plate). After partial charging or repeated charging and discharging, the electrode plate is pressurized to a thickness of approximately Q 5 rran to obtain a completed electrode plate.
このようにして得られた極板を、厚さαδ閣の焼結式ニ
ッケル正極板と、ナイロン不織布からなるセパレータと
を組合せて単３形の密閉型ニッケル・カドミウム蓄電池
を作成し、充電を行なって水素発生状態を従来の負極板
と比較した。なお、試験電池は負極以外はすべて同一と
した。The thus obtained electrode plate was combined with a sintered nickel positive electrode plate having a thickness of αδ and a separator made of nylon nonwoven fabric to create an AA sealed nickel-cadmium storage battery, and the battery was charged. The hydrogen generation state was compared with that of a conventional negative electrode plate. The test batteries were all the same except for the negative electrode.
この結果、本発明の負極板を用いた電池の場合、水素発
生までに充電した電気量が、従来の負極板を用いた電池
に比べて多いことがわかった。このことは負極板の利用
率が向上したことを示している。As a result, it was found that in the case of a battery using the negative electrode plate of the present invention, the amount of electricity charged before hydrogen generation was greater than in a battery using a conventional negative electrode plate. This indicates that the utilization rate of the negative electrode plate has improved.
また、第２図で示すように、ニッケル塩添加の効果は、
化成後の水酸化ニッケルの状態において、重量比で酸化
カドミウム１００部に対しＱ２部から実験的に確認され
たが、その原因の詳細については不明である。また、１
０重量部以上では極板の硬化がはなはだしくなり、電池
構成に支障をきたすのでさけた方がよい。In addition, as shown in Figure 2, the effect of adding nickel salt is
In the state of nickel hydroxide after chemical formation, this was experimentally confirmed from 2 parts of Q2 to 100 parts of cadmium oxide by weight, but the details of the cause are unknown. Also, 1
If the amount is more than 0 parts by weight, the hardening of the electrode plate will be severe and the battery structure will be affected, so it is better to avoid it.
７ページ
なお、本実施例ではニッケル塩を硫酸ニッケルとしたが
、ニッケル塩は塩化ニッケル、スルフアミノ酸ニッケル
等化成時のアルカリ処理にて水酸化ニッケル化するもの
なら何んでもよい。特にスルフアミノ酸ニッケルの場合
、利用率として最大のものが得られた。In this example, the nickel salt was nickel sulfate, but the nickel salt may be any salt that can be converted into nickel hydroxide during alkali treatment during chemical formation, such as nickel chloride or nickel sulfur amino acid. In particular, in the case of nickel sulfamino acid, the highest utilization rate was obtained.
以」二のように本発明は、ペースト式負極板をニッケル
塩溶液中に浸漬することで含浸添加し、ついで化成して
水酸化ニッケルとすることにより、負極活物質の利用率
を向上させることができたものである。As described above, the present invention improves the utilization rate of the negative electrode active material by immersing a paste-type negative electrode plate in a nickel salt solution to impregnate and add nickel, and then chemically converting it into nickel hydroxide. This is what was created.
第１図は本発明の実施例によるアルカリ蓄電池用カドミ
ウム負極における利用率を示す図、第２図はニッケル塩
添加量と利用率との関係を示したものである。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名１１
１
第１図
ｉ 糧ｔ’ｌ “）ヨＩ 牢（％ン
第２図FIG. 1 is a diagram showing the utilization rate of a cadmium negative electrode for an alkaline storage battery according to an example of the present invention, and FIG. 2 is a diagram showing the relationship between the amount of nickel salt added and the utilization rate. Name of agent: Patent attorney Toshio Nakao and 1 other person11
1 Figure 1 I food t'l ``)yoI prison (%n Figure 2
Claims (2)
着剤溶液とを加えて練合したペース）ｋ芯材に塗着、乾
燥したのち、ニッケル塩溶液に浸漬し、乾燥後アルカリ
水溶液中で化成することを特徴とする蓄電池用カドミウ
ム負極板の製造方法。(1) A paste made by using cadmium oxide as an active material and adding a conductive agent and a binder solution to it and kneading it) After applying it to the core material and drying it, immerse it in a nickel salt solution, and after drying, add it to an alkaline aqueous solution. A method for manufacturing a cadmium negative electrode plate for a storage battery, characterized in that a cadmium negative electrode plate is chemically formed inside the cell.
酸化ニッケルの状態において重量比で酸化カドミウム１
００部に対して６２〜１０部である特許請求の範囲第１
項記載のアルカリ蓄電池用カドミウム負極板の製造方法
。(2) The amount of nickel salt added by the immersion is 1 part by weight of cadmium oxide in the state of nickel hydroxide after chemical formation.
Claim 1 which is 62 to 10 parts to 00 parts
A method for producing a cadmium negative electrode plate for an alkaline storage battery as described in 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57081915A JPS58198856A (en) | 1982-05-14 | 1982-05-14 | Manufacture of negative cadmium plate for alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57081915A JPS58198856A (en) | 1982-05-14 | 1982-05-14 | Manufacture of negative cadmium plate for alkaline storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58198856A true JPS58198856A (en) | 1983-11-18 |
Family
ID=13759741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57081915A Pending JPS58198856A (en) | 1982-05-14 | 1982-05-14 | Manufacture of negative cadmium plate for alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58198856A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62264557A (en) * | 1986-05-13 | 1987-11-17 | Toshiba Corp | Metal oxide-hydrogen battery |
| JPS63310564A (en) * | 1987-06-12 | 1988-12-19 | Matsushita Electric Ind Co Ltd | Manufacture of paste type cadmium negative electrode |
| US5264309A (en) * | 1991-01-10 | 1993-11-23 | Sorapec S.A. | Cadmium electrodes for alkaline batteries |
| FR2940529A1 (en) * | 2008-12-24 | 2010-06-25 | Saft Groupe Sa | NEGATIVE ELECTRODE ACTIVE MATERIAL OF NICKEL-CADMIUM GENERATOR. |
-
1982
- 1982-05-14 JP JP57081915A patent/JPS58198856A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62264557A (en) * | 1986-05-13 | 1987-11-17 | Toshiba Corp | Metal oxide-hydrogen battery |
| JPH0810596B2 (en) * | 1986-05-13 | 1996-01-31 | 株式会社東芝 | Metal oxide / hydrogen battery |
| JPS63310564A (en) * | 1987-06-12 | 1988-12-19 | Matsushita Electric Ind Co Ltd | Manufacture of paste type cadmium negative electrode |
| JPH0831315B2 (en) * | 1987-06-12 | 1996-03-27 | 松下電器産業株式会社 | Method for producing paste type cadmium negative electrode |
| US5264309A (en) * | 1991-01-10 | 1993-11-23 | Sorapec S.A. | Cadmium electrodes for alkaline batteries |
| US5334465A (en) * | 1991-01-10 | 1994-08-02 | Sorapec S.A. | Method of making cadmium electrodes for alkaline batteries |
| FR2940529A1 (en) * | 2008-12-24 | 2010-06-25 | Saft Groupe Sa | NEGATIVE ELECTRODE ACTIVE MATERIAL OF NICKEL-CADMIUM GENERATOR. |
| WO2010073227A1 (en) * | 2008-12-24 | 2010-07-01 | Saft Groupe S.A. | Active material for the negative electrode of a nickel-cadmium generator |
| US8889296B2 (en) | 2008-12-24 | 2014-11-18 | Saft Groupe Sa | Active material of a nickel-cadmium generator negative electrode |
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